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BY-PRODUCT AND CONTROL IN AMMONIA PROCESS
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Prem Baboo
The Institution of Engineers (India)
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BY-PRODUCT AND CONTROL IN AMMONIA PROCESS
By
Prem Baboo
Rtd. From National Fertilizers, India
&
Dangote Fertilizers Ltd, Nigeria
Abstract
In Ammonia plant numbers unwanted
products are formed such as CO2 &
methanol, Methanol is the by-product and it
is very dangerous for environment and
cations and anion resin also, which is used
treated waste water through urea plant.
Methanol is also dangerous for Ozone
layers.CO2 is also by-product in ammonia
process but it is used for production of urea.
The paper intended how it is generate in
ammonia plant as a by-product.how to control
and minimized. How does this damage the
environment? It is desirable to minimize
methanol by-product formention for several
reasons: Methanol emissions are being
regulated to protect the environment. Several
ammonia plants are already facing regulations
that limit methanol emissions to the atmosphere.
These regulations affect plants that vent the CO2
stream as well as plants that are not designed to
recover methanol from the various vents. The
methanol recovers from CO2 compressor
separators are using in anaerobic water treatment
plant as bacteria feed.
Keyword
Methanol, environment, ammonia , Ozone,
Introduction
In ammonia plant CO shift conversion section
the entire CO converted into CO2 which is used
for urea production .In ammonia plant generally
two or three CO shift converter are used HT/MT
and LT. Ammonia and hydrogen plant operators
are becoming increasingly concerned with
methanol byproduct formation in their plants.
Methanol formation takes place over the
copperbased low-temperature-shift (LTS)
catalyst according to the following reaction
scheme:
CO + 2H2 ↔ CH3OH Reaction (1)
(∆H = -91 kJ/mol; ∆G = -25.34 kJ/mol)
Hydrogenation of Carbon dioxide
CO2 + 3H2 ↔ CH3OH + H2O Reaction (2)
(∆H = -49.5 kJ/mol; ∆G = 3.30 kJ/mol)
Water gas shift reaction
CO + H2O ↔ CO2 + H2 Reaction (3)
(∆H = -41.2 kJ/mol; ∆G = -28.60 kJ/mol)
New regulations national & international
restricting the allowable levels of methanol
emissions from ammonia plant is being
implemented in many countries worldwide. In
particular, plants in the India. are faced with
severe restrictions with respect to methanol
emissions. It is possible to reduce methanol by-
product formation in some methanol plants by
adjusting the LTS operating conditions. In most
cases, however, the plants will be forced to
implement more drastic means of reducing
methanol by-product formation and/or
emissions. Although removal of methanol from
the various vent gases requires large investments
and installation of additional equipment in the
plant, the use of a more selective LTS catalyst
may be a low-cost, highly effective alternative
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solution, as illustrated in this article. A new LTS
that significantly reduces methanol formation
has been developed, enabling ammonia and
hydrogen plants to comply with regula
.
Fig-1
Description of the Process
There are two shift converter are used to convert
CO to CO2.The process gas is cooled down to
about 360°C by generating steam in
heat boiler before entering the HT CO converter
. The temperature is controlled by TIC
the internal bypass of heat exchanger
optimum inlet temperature, i.e. the inlet
temperature at which CO slip is at a minimum,
depends on the actual catalyst activity. With
fresh catalyst it is normally best to operate at a
temperature somewhat lower than the design
temperature. As the catalyst ages, the
temperature should be increased. The normal
operating range is 330-450°C. The catalyst is
still somewhat active down to a temperature of
300°C. While continuous operation is permitted
at hot spot temperatures up to 470°C, there is
some loss in activity at higher temperatures. Do
not exceed the reactor design temperature of
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solution, as illustrated in this article. A new LTS catalyst
ntly reduces methanol formation
has been developed, enabling ammonia and
ants to comply with regulations
without undertaking major investments in new
equipment
used to convert
The process gas is cooled down to
about 360°C by generating steam in the waste
g the HT CO converter
re is controlled by TIC adjusting
the internal bypass of heat exchanger. The
let temperature, i.e. the inlet
temperature at which CO slip is at a minimum,
depends on the actual catalyst activity. With
fresh catalyst it is normally best to operate at a
temperature somewhat lower than the design
temperature. As the catalyst ages, the inlet
temperature should be increased. The normal
450°C. The catalyst is
still somewhat active down to a temperature of
300°C. While continuous operation is permitted
at hot spot temperatures up to 470°C, there is
ity at higher temperatures. Do
not exceed the reactor design temperature of
480°C. The temperature increase in
be around 76°C, depending on the actual
steam/dry gas ratio.
Residual CO
During normal operation, the CO c
outlet of HT should be 3.49 dry mole%. As the
shift catalyst ages and the activity decreases, the
approach to the equilibrium increases. The
reaction coefficient (Kp) can be determined on
the basis of an analysis of the gas leaving the
converter. The value of Kp can be
using the equation below. With Kp as input, the
equilibrium temperature can be found in the shift
reaction .
𝐾𝑃 =
mole% CO2 ∗ mole
2𝑎mole% CO ∗ mole
The difference between the equilibrium
temperature and the actual temperature, the
temperature approach to equilibrium, is an
indication of the catalyst activity.
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without undertaking major investments in new
480°C. The temperature increase in HT should
be around 76°C, depending on the actual
During normal operation, the CO content at the
hould be 3.49 dry mole%. As the
shift catalyst ages and the activity decreases, the
approach to the equilibrium increases. The
reaction coefficient (Kp) can be determined on
the basis of an analysis of the gas leaving the
of Kp can be calculated
using the equation below. With Kp as input, the
equilibrium temperature can be found in the shift
mole% H 2
mole% H 2 O
The difference between the equilibrium
temperature and the actual temperature, the
temperature approach to equilibrium, is an
indication of the catalyst activity.
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LT CO Converter
After leaving the HT CO converter, the process
gas cools down as it passes through
heat boiler ( and the methanator trim heater
parallel, and BFW pre-heaters. The temperature
at the inlet of the LT CO converter
205°C, is controlled by the process g
on TIC. As for the HT CO converter, the
optimum inlet temperature, i.e. the inlet
temperature at which CO slip is at a minimum,
depends on the actual catalyst activity. With a
fresh catalyst it is normally best to operate at a
temperature somewhat lower than the design
temperature. As the catalyst ages, the inlet
temperature should be increased. The normal
operating range is 170-250°C; do not exceed the
Fig-2
Effect of Methanol Emissions on the
Environment
Acute Effects:
Acute exposure of humans to methanol by
inhalation or ingestion may result in visual
disturbances, such as blurred or dimness of
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After leaving the HT CO converter, the process
gas cools down as it passes through the waste
ethanator trim heater in
. The temperature
f the LT CO converter, normally
205°C, is controlled by the process gas bypass
. As for the HT CO converter, the
optimum inlet temperature, i.e. the inlet
ure at which CO slip is at a minimum,
depends on the actual catalyst activity. With a
fresh catalyst it is normally best to operate at a
temperature somewhat lower than the design
temperature. As the catalyst ages, the inlet
. The normal
250°C; do not exceed the
reactor design temperature of 300°C. The
temperature increase should be around 24°C,
depending on the conversion in the HT CO
converter and on the steam/dry gas ratio.
Condensing steam is harmful
the inlet temperature should always be at least
15-20°C above the dew point of the gas. There is
a risk that condensate will form on th
surface of heat exchangers.
Residual CO
During normal operations, the CO content outlet
11-R-205 should be approximately 0.33 dry
mole%. To evaluate the activity of the LT shift
catalyst, follow the same procedure as described
above.
anol Emissions on the
Acute exposure of humans to methanol by
inhalation or ingestion may result in visual
disturbances, such as blurred or dimness of
vision, leading to blindness.
damage, specifically permanent motor
dysfunction, may also result.
with methanol can produce mild dermatitis in
humans. Tests involving acute exposure of rats,
mice, and rabbits have demonstrated methanol to
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reactor design temperature of 300°C. The
temperature increase should be around 24°C,
depending on the conversion in the HT CO
converter and on the steam/dry gas ratio.
to the catalyst, so
the inlet temperature should always be at least
20°C above the dew point of the gas. There is
a risk that condensate will form on the cold
During normal operations, the CO content outlet
205 should be approximately 0.33 dry
mole%. To evaluate the activity of the LT shift
catalyst, follow the same procedure as described
vision, leading to blindness. Neurological
damage, specifically permanent motor
nction, may also result. Contact of skin
e mild dermatitis in
Tests involving acute exposure of rats,
mice, and rabbits have demonstrated methanol to
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have low acute toxicity from oral or inhalation
exposure, and moderate acute toxicity from
dermal exposure.
Chronic Effects
Chronic inhalation or oral exposure to methanol
may result in headache, dizziness, giddiness,
insomnia, nausea, gastric disturbances,
conjunctivitis, visual disturbances (blurred
vision), and blindness in humans. Elevated
levels of liver enzymes and decreased brain
weight were observed in rats chronically
exposed to methanol via gavage (experimentally
placing the chemical in the stomach). EPA has
not established a Reference Concentration
(RFC) for methanol. The Reference Dose (RfD)
for methanol is 0.5 milligrams per kilogram
body weight per day (mg/kg/d) based on
increased liver enzymes (SAP and SGPT) and
decreased brain weight in rats. The RFD is an
estimate (with uncertainty spanning perhaps an
order of magnitude) of a daily oral exposure to
the human population (including sensitive
subgroups) that is likely to be without
appreciable risk of deleterious non cancer effects
during a lifetime. It is not a direct estimator of
risk but rather a reference point to gauge the
potential effects. At exposures increasingly
greater than the RfD, the potential for adverse
health effects increases. Lifetime exposure
above the RfD does not imply that an adverse
health effect would necessarily occur.
Effect on Ozone Layers
Ground-level ozone is formed from nitrous
oxides under the influence of the ultraviolet
(UV) radiation of the sun. Nitrogen dioxide
(NO2), emitted by combustion processes into the
at mosphere, is split by UV radiation into
nitrogen monoxide (NO) and an oxygen atom.
This atomic oxygen combines with an oxygen
molecule, forming ozone (O3): Methanol is a
widely used solvent and a potential fuel for
motor vehicles. Following Methanol product are
dangerous for Ozone Layer. Besides
environmental aspects, there is also an economic
driver to reduce methanol formation by the
process, at least to the extent that additional
costs are not prohibitive. Methanol formation in
the CO shift consumes hydrogen which would
otherwise be used to make ammonia. In broad
terms, every tone of methanol that is formed
(and not recovered to the reformer feed via the
process condensate stripper) results in a loss of
1.1 tone of ammonia. This loss in its own right
can be a powerful incentive for installing a
selective LTS catalyst such as KATALCOJM
83-3X. In addition, methanol is an oxygen
containing component which must be removed
from the process gas before it is fed to the
ammonia synthesis. This removal is normally
achieved in the Methanation by reaction with
hydrogen. Stripping of process condensate is a
very economical way to reduce the methanol
content in the process condensate to make it
ready for reuse as make-up water to the
demineralization unit, thus reducing raw water
consumption.
Comparison of Operating Costs
If the ammonia plant is coupled to an adjacent
urea plant, the majority of the methanol
containing CO2 stream is used as feed to the
urea plant. In such a situation it does not lead to
emissions during normal operation of the
complex. If the authorities allow emissions for
the limited amount of time of the year whilst the
urea plant is not in operation, an “end-of-pipe”
methanol reduction system as described above
might be designed only for the quantity of CO2
vented during normal operation. This allowance
can lead to a significant cost advantage when
compared to the systems described above which
are fully integrated into the ammonia process
and which ensure a low methanol concentration
for the full amount of CO2. In this case they
have to be designed for the full flowrate of
process gas, with no reduction in size being
possible. The economics of a process which
absorbs the methanol from the CO2 stream
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downstream the regenerator in the CO2 removal
unit, depends on the following decisions: For a
simple system, there is just a bleed stream and a
make-up by fresh water. Possibly, the CO2 of
stream 8 is cooled below ambient temperature to
condense as much liquid as possible. A more
complex system would contain an additional
absorber installed in stream no. 9 and a
desorption for example by sending the water to
the already existing condensate stripper. If an
“end-of-pipe” system has to be designed for the
maximum possible amount of CO2 vented, it
will need to operate at 5 to 6% of capacity most
of the time (basis: 2,200 MTPD ammonia plant
with a 3,500 MTPD urea plant) and will
experience 100% load only a few times per year.
The favored option might be different for a new
project than a retrofit. In the first case, one is
free to design the plant right from the beginning
for low emission figures. In the latter case, it can
be difficult to accommodate changes in process
temperatures due to limitations in space for
additional equipment or availability of utilities
Emission reductions inevitably require
additional investment and lead to increased
energy consumption. With the exception of the
benefits that can be obtained through the use of
use of selective LTS catalysts, there is little
economic incentive to reduce methanol
emissions. None of the removal or abatement
systems convert the methanol into a valuable
product, but all of them consume energy, as
highlighted in Table 1.
Sr. No. Parameters Observation &Results
1 Lower temperature at condensate separator
(cooling with CW)
More condensate to be stripped.
More cooling water needed
2 Lower temperature at condensate separator
(cooling with chillers)
More condensate to be stripped.
More cooling water needed
Chilling duty is needed (electric power /
steam)
3 Catalytic methanol removal at vent Methanol is combusted and CO2 is formed by
this process
Air blower needed (electric power)
Table -1
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Table –2
How to Control Methanol formation in
ammonia plant
The Methanol comes in urea plant by CO
It is 80% separated by CO2 compressor 1
3rd
stage separators.20 % carryover through CO
and it goes to waste water section, treated water
waste contains about 150-200 ppm methanol. it
is very dangerous for cations and anaions resin,
it can damage resins. Shift reaction in Line
carried out three steps (HT/MT/LT) an
line-2 2 Two steps (HT/LT) no MT is line
Urea line-2 HT inlet/outlet temperatures are
355/430 degree cent. Iron oxide catalyst is used.
In LT Cu based catalyst is used, Inle
temp are-195/212 degree cent . Sulpher &
Chlorides are poison for catalyst. Chromium
based catalyst on top of the first bed, which will
act as a chlorine guard catalyst, while the
remaining will be made up of alumina based
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How to Control Methanol formation in
The Methanol comes in urea plant by CO2 rout.
compressor 1st
,2nd
&
stage separators.20 % carryover through CO2
and it goes to waste water section, treated water
200 ppm methanol. it
is very dangerous for cations and anaions resin,
ins. Shift reaction in Line -1
ed out three steps (HT/MT/LT) and that of
2 2 Two steps (HT/LT) no MT is line-2.In
2 HT inlet/outlet temperatures are
355/430 degree cent. Iron oxide catalyst is used.
In LT Cu based catalyst is used, Inlet/outlet
195/212 degree cent . Sulpher &
Chlorides are poison for catalyst. Chromium
based catalyst on top of the first bed, which will
act as a chlorine guard catalyst, while the
remaining will be made up of alumina based
catalyst. The catalyst consists of oxides of
copper, zinc, and chromium or alumina.
Reading for methanol in Urea line
Fertilizers Ltd. Vijaipur)
1st
separator-2122 ppm
2nd
separator-860 ppm
3rd
separator-255 ppm
Waste water treated water 166 ppm.
In urea Line-1 Methanol produced very less.
Here the three CO shift converter are used.
The methanol generally unwanted by
LTS CO shift converter. when catalyst activity
of LTS goes down it can be formed it can be
controlled by LTS catalyst.
developed by both the M/S Haldor Topsoe
(Catalyst LK-821-2, LK823) is promoted by
caesium which efficiently reduced
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onsists of oxides of
copper, zinc, and chromium or alumina.
in Urea line-2 (National
Waste water treated water 166 ppm.
ol produced very less.
Here the three CO shift converter are used.
unwanted by product in
LTS CO shift converter. when catalyst activity
of LTS goes down it can be formed it can be
The LTS catalyst
developed by both the M/S Haldor Topsoe
2, LK823) is promoted by
caesium which efficiently reduced
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MeOH. The methanol is inversely proportional
to temperature. M/S Haldor topsoe and KBR
developed advance catalyst if problem then
contact to licenser and catalyst may be changed.
The MeoH generally formed predominately over
the LTS catalyst and part of it end in the process
condensate stripper.
Following are the method to reduced by
methanol
1. Temp of LTS to be minimum
2. Reduced catalyst Volume.
3. Catalyst promoters to be used
4. Avoid Aged catalyst.
5. CO concentration should be lower in
LTS feed.
Fig- 3
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The methanol is inversely proportional
to temperature. M/S Haldor topsoe and KBR
developed advance catalyst if problem then may
contact to licenser and catalyst may be changed.
The MeoH generally formed predominately over
the LTS catalyst and part of it end in the process
reduced by- product
emp of LTS to be minimum.
Catalyst promoters to be used.
CO concentration should be lower in
6. Lower operation pressure.
7. High Steam/dry gas ratio
8. Higher space velocity
the methanol concentration leaving the HTS
catalyst is close to equilibrium and therefore
independent of catalyst type, methanol
formation in LTS catalysts is kinetically
limited and does not usually reach
equilibrium. As the methanol forming
reaction is exothermic, and HTS catalysts
operate at higher temperature and at high
temperature methanol formation is less
shape of the equilibrium curve dictates that
methanol formation across HTS catalysts is
substantially less than that across traditional,
nonselective LTS catalysts (Figure 3).
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Lower operation pressure.
High Steam/dry gas ratio.
methanol concentration leaving the HTS
catalyst is close to equilibrium and therefore
independent of catalyst type, methanol
formation in LTS catalysts is kinetically
limited and does not usually reach
equilibrium. As the methanol forming
hermic, and HTS catalysts
operate at higher temperature and at high
temperature methanol formation is less the
shape of the equilibrium curve dictates that
methanol formation across HTS catalysts is
substantially less than that across traditional,
catalysts (Figure 3).
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LTS catalyst is slightly unusual in that
selectivity increases, and by-product formation
decreases, as the catalyst ages (Figure 4). This
behavior is because the activity with regard to
methanol synthesis declines as the active sites
Fig-4
Process Condensate Treatment
The gas leaving the LTS is cooled and
condensate is removed via the process
condensate separator. The split of methanol is
determined by vapor-liquid equilibrium, hence
the lower the temperature, the greater the
proportion of methanol that is removed via t
process condensate, as illustrated in Figure 5.
Modern plants, and older plants retrofitted with
condensate strippers in the last couple of
decades, use a medium pressure stripper to treat
the condensate. A well designed stripper meets
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LTS catalyst is slightly unusual in that
product formation
Figure 4). This
is because the activity with regard to
methanol synthesis declines as the active sites
for methanol synthesis decrease. There is no
corresponding impact on the activity with regard
to the shift reaction, which, in a well
catalyst, remains high enough to maintain an
equilibrium CO slip.
The gas leaving the LTS is cooled and
condensate is removed via the process
condensate separator. The split of methanol is
liquid equilibrium, hence
the lower the temperature, the greater the
proportion of methanol that is removed via the
in Figure 5.
Modern plants, and older plants retrofitted with
condensate strippers in the last couple of
decades, use a medium pressure stripper to treat
the condensate. A well designed stripper meets
most environmental standards for waste water
and will recycle methanol to the reformer feed.
Plants with older designs of stripper can use LP
stripping to remove methanol and ammonia from
the condensate. Sometimes they are vented to
atmosphere along with the stripping ste
more commonly the vent stream is condensed
and sent, for example, to a feed coil saturator
(although sometimes a small, methanol
containing stream is “purged” to atmosphere).
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for methanol synthesis decrease. There is no
corresponding impact on the activity with regard
to the shift reaction, which, in a well-structured
enough to maintain an
al standards for waste water
and will recycle methanol to the reformer feed.
Plants with older designs of stripper can use LP
stripping to remove methanol and ammonia from
the condensate. Sometimes they are vented to
atmosphere along with the stripping steam, but
more commonly the vent stream is condensed
and sent, for example, to a feed coil saturator
(although sometimes a small, methanol
containing stream is “purged” to atmosphere).
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Fig-5
Methanol Emission Reduction
Overview several options exist for reducing
methanol emissions including the following:
1. Reducing the amount that is formed.
2. Removal or decomposition of the methanol
within the process.
3. Removal or decomposition at the point of
emission.
4. Combination of the above schemes.
Reduction of Methanol Formation
The amount of by-product methanol produced in
the LTS converter is influenced by a variety of
factors, which are summarized in Table
Sr.
No.
Increase in Effect on methanol
make
1 Steam / H2 ratio Decrease
2 Inlet
temperature
↑(if not at
equilibrium)
↓(if at equilibrium)
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options exist for reducing
methanol emissions including the following:
ing the amount that is formed.
Removal or decomposition of the methanol
tion at the point of
the above schemes.
Reduction of Methanol Formation
product methanol produced in
the LTS converter is influenced by a variety of
in Table 1. In
most plants, there is only limited flexibility to
change operating conditions with the result that
LTS catalyst selection is the only real alternative
for reducing methanol by-product formation.
Selective low methanol LTS catalysts such as
KATALCOJM 83-3X, reduce methanol
formation by about 90% compared to
conventional non-selective LTS catalysts. As the
relative contribution to methanol formation from
the LTS falls, that from the HTS increases, and
methanol emissions can be grossly
underestimated if formation across a selective
LTS is considered in isolation
Effect on methanol
Decrease
↑(if not at
equilibrium)
↓(if at equilibrium)
3 Pressure ↑Increase
4 Space velocity ↓Decrease
5 Catalyst age ↓Decrease
6 Catalyst
selectivity
↓Decrease
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most plants, there is only limited flexibility to
conditions with the result that
LTS catalyst selection is the only real alternative
product formation.
Selective low methanol LTS catalysts such as
3X, reduce methanol
formation by about 90% compared to
selective LTS catalysts. As the
relative contribution to methanol formation from
the LTS falls, that from the HTS increases, and
methanol emissions can be grossly
underestimated if formation across a selective
LTS is considered in isolation (Figure 6).
↑Increase
↓Decrease
↓Decrease
↓Decrease
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Table-3(Effect of various operating parameters
Fig-6
Separated methanol from CO2
separators used as a bacteria Feed in waste
water anaerobic Treatment
In CO2 compressor separators about 80%
methanol can be used in waste water treatment
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(Effect of various operating parameters on methanol production)
compressor
used as a bacteria Feed in waste
compressor separators about 80%
methanol can be used in waste water treatment
as a Bactria feed as shown in the figure
1st
separator contain maximum methanol.
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as a Bactria feed as shown in the figure- 7.The
separator contain maximum methanol.
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Fig-7
Conclusion
In Urea Plant 1st
separator, if pressure and
tempearure maintain according methanol
separation then you can remove 80
methanol from separators. As with oth
organic compounds emissions, methanol
emissions from ammonia plants are considered
to contribute to ground-level
Consequently, in many places of the world,
targets and regulations exist to reduce Volatile
organic compound emissions. Regu
starting to pay more attention to Volatile organic
compound emissions on ammonia plants and
this trend is likely to increase. Several technical
options exist to reduce these emissions,
including the following:
1. Reducing methanol by
formation in the LTS catalyst.
2. Modifying the CO2 removal process.
3. End-of-pipe solution.
Lowest Volatile organic compound
can be achieved only by catalytic conversion at
the point of emission. However, by
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if pressure and
tempearure maintain according methanol
separation then you can remove 80-85%
As with other Volatile
emissions, methanol
sions from ammonia plants are considered
level ozone.
s of the world,
t to reduce Volatile
emissions. Regulators are
ing to pay more attention to Volatile organic
emissions on ammonia plants and
o increase. Several technical
options exist to reduce these emissions,
Reducing methanol by-product
formation in the LTS catalyst.
Modifying the CO2 removal process.
Lowest Volatile organic compound emissions
can be achieved only by catalytic conversion at
the point of emission. However, by combining it
with the other options, the amount of methanol
to be converted in the emission stre
reduced. Since the Volatile organic compound
emissions are influenced by sev
parameters and catalyst properties, one should
not prematurely decide on one tech
solution. It is recommended to look at the
process in close co-operation with the catalyst
vendor, CO2 removal licensor, and overall
process licensor and contractor, in order to
obtain the best overall solution
References
1. “Development of a Predictive Kinetic Model for
Methanol Formation over Low Temperature
Shift Catalysts”, P V Broadhurst, C Park and I
Johnston, Proceedings of Nitrogen 2006,
Vienna, 12-15 March 2006.
2. United States Environmental Protection Agency,
New Source Review (NSR) Improvements:
Supplemental Analysis of the Environmental
Impact of the 2002 Final NSR Improvement
Rules, November 2002 [6] Clean Air Act,
Section 112.
27th
Mar. 2022
Research Gate is an academic social networking site
ite for scientists and researchers
tions, the amount of methanol
to be converted in the emission stream can be
reduced. Since the Volatile organic compound
luenced by several process
parameters and catalyst properties, one should
prematurely decide on one technical
solution. It is recommended to look at the
operation with the catalyst
removal licensor, and overall
icensor and contractor, in order to
obtain the best overall solution.
“Development of a Predictive Kinetic Model for
Methanol Formation over Low Temperature
Shift Catalysts”, P V Broadhurst, C Park and I
ceedings of Nitrogen 2006,
United States Environmental Protection Agency,
New Source Review (NSR) Improvements:
Supplemental Analysis of the Environmental
Impact of the 2002 Final NSR Improvement
Rules, November 2002 [6] Clean Air Act,
View publication stats
View publication stats

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BY-PRODUCT AND CONTROL IN AMMONIA PROCESS.pdf

  • 1. See discussions, stats, and author profiles for this publication at: https://www.researchgate.net/publication/359501912 BY-PRODUCT AND CONTROL IN AMMONIA PROCESS Presentation · March 2022 CITATIONS 0 1 author: Some of the authors of this publication are also working on these related projects: Comparison Stamicarbon Saipem View project Industrial Process View project Prem Baboo The Institution of Engineers (India) 83 PUBLICATIONS   17 CITATIONS    SEE PROFILE All content following this page was uploaded by Prem Baboo on 27 March 2022. The user has requested enhancement of the downloaded file.
  • 2. www.researchgate.net 27th Mar. 2022 Research Gate is an academic social networking site This is an open access article, Research Gate is a European commercial social networking site for scientists and researchers BY-PRODUCT AND CONTROL IN AMMONIA PROCESS By Prem Baboo Rtd. From National Fertilizers, India & Dangote Fertilizers Ltd, Nigeria Abstract In Ammonia plant numbers unwanted products are formed such as CO2 & methanol, Methanol is the by-product and it is very dangerous for environment and cations and anion resin also, which is used treated waste water through urea plant. Methanol is also dangerous for Ozone layers.CO2 is also by-product in ammonia process but it is used for production of urea. The paper intended how it is generate in ammonia plant as a by-product.how to control and minimized. How does this damage the environment? It is desirable to minimize methanol by-product formention for several reasons: Methanol emissions are being regulated to protect the environment. Several ammonia plants are already facing regulations that limit methanol emissions to the atmosphere. These regulations affect plants that vent the CO2 stream as well as plants that are not designed to recover methanol from the various vents. The methanol recovers from CO2 compressor separators are using in anaerobic water treatment plant as bacteria feed. Keyword Methanol, environment, ammonia , Ozone, Introduction In ammonia plant CO shift conversion section the entire CO converted into CO2 which is used for urea production .In ammonia plant generally two or three CO shift converter are used HT/MT and LT. Ammonia and hydrogen plant operators are becoming increasingly concerned with methanol byproduct formation in their plants. Methanol formation takes place over the copperbased low-temperature-shift (LTS) catalyst according to the following reaction scheme: CO + 2H2 ↔ CH3OH Reaction (1) (∆H = -91 kJ/mol; ∆G = -25.34 kJ/mol) Hydrogenation of Carbon dioxide CO2 + 3H2 ↔ CH3OH + H2O Reaction (2) (∆H = -49.5 kJ/mol; ∆G = 3.30 kJ/mol) Water gas shift reaction CO + H2O ↔ CO2 + H2 Reaction (3) (∆H = -41.2 kJ/mol; ∆G = -28.60 kJ/mol) New regulations national & international restricting the allowable levels of methanol emissions from ammonia plant is being implemented in many countries worldwide. In particular, plants in the India. are faced with severe restrictions with respect to methanol emissions. It is possible to reduce methanol by- product formation in some methanol plants by adjusting the LTS operating conditions. In most cases, however, the plants will be forced to implement more drastic means of reducing methanol by-product formation and/or emissions. Although removal of methanol from the various vent gases requires large investments and installation of additional equipment in the plant, the use of a more selective LTS catalyst may be a low-cost, highly effective alternative
  • 3. www.researchgate.net This is an open access article, Research Gate is a European commercial social networking s solution, as illustrated in this article. A new LTS that significantly reduces methanol formation has been developed, enabling ammonia and hydrogen plants to comply with regula . Fig-1 Description of the Process There are two shift converter are used to convert CO to CO2.The process gas is cooled down to about 360°C by generating steam in heat boiler before entering the HT CO converter . The temperature is controlled by TIC the internal bypass of heat exchanger optimum inlet temperature, i.e. the inlet temperature at which CO slip is at a minimum, depends on the actual catalyst activity. With fresh catalyst it is normally best to operate at a temperature somewhat lower than the design temperature. As the catalyst ages, the temperature should be increased. The normal operating range is 330-450°C. The catalyst is still somewhat active down to a temperature of 300°C. While continuous operation is permitted at hot spot temperatures up to 470°C, there is some loss in activity at higher temperatures. Do not exceed the reactor design temperature of Research Gate is an academic social networking site This is an open access article, Research Gate is a European commercial social networking site for scientists and researchers solution, as illustrated in this article. A new LTS catalyst ntly reduces methanol formation has been developed, enabling ammonia and ants to comply with regulations without undertaking major investments in new equipment used to convert The process gas is cooled down to about 360°C by generating steam in the waste g the HT CO converter re is controlled by TIC adjusting the internal bypass of heat exchanger. The let temperature, i.e. the inlet temperature at which CO slip is at a minimum, depends on the actual catalyst activity. With fresh catalyst it is normally best to operate at a temperature somewhat lower than the design temperature. As the catalyst ages, the inlet temperature should be increased. The normal 450°C. The catalyst is still somewhat active down to a temperature of 300°C. While continuous operation is permitted at hot spot temperatures up to 470°C, there is ity at higher temperatures. Do not exceed the reactor design temperature of 480°C. The temperature increase in be around 76°C, depending on the actual steam/dry gas ratio. Residual CO During normal operation, the CO c outlet of HT should be 3.49 dry mole%. As the shift catalyst ages and the activity decreases, the approach to the equilibrium increases. The reaction coefficient (Kp) can be determined on the basis of an analysis of the gas leaving the converter. The value of Kp can be using the equation below. With Kp as input, the equilibrium temperature can be found in the shift reaction . 𝐾𝑃 = mole% CO2 ∗ mole 2𝑎mole% CO ∗ mole The difference between the equilibrium temperature and the actual temperature, the temperature approach to equilibrium, is an indication of the catalyst activity. 27th Mar. 2022 Research Gate is an academic social networking site ite for scientists and researchers without undertaking major investments in new 480°C. The temperature increase in HT should be around 76°C, depending on the actual During normal operation, the CO content at the hould be 3.49 dry mole%. As the shift catalyst ages and the activity decreases, the approach to the equilibrium increases. The reaction coefficient (Kp) can be determined on the basis of an analysis of the gas leaving the of Kp can be calculated using the equation below. With Kp as input, the equilibrium temperature can be found in the shift mole% H 2 mole% H 2 O The difference between the equilibrium temperature and the actual temperature, the temperature approach to equilibrium, is an indication of the catalyst activity.
  • 4. www.researchgate.net This is an open access article, Research Gate is a European commercial social networking s LT CO Converter After leaving the HT CO converter, the process gas cools down as it passes through heat boiler ( and the methanator trim heater parallel, and BFW pre-heaters. The temperature at the inlet of the LT CO converter 205°C, is controlled by the process g on TIC. As for the HT CO converter, the optimum inlet temperature, i.e. the inlet temperature at which CO slip is at a minimum, depends on the actual catalyst activity. With a fresh catalyst it is normally best to operate at a temperature somewhat lower than the design temperature. As the catalyst ages, the inlet temperature should be increased. The normal operating range is 170-250°C; do not exceed the Fig-2 Effect of Methanol Emissions on the Environment Acute Effects: Acute exposure of humans to methanol by inhalation or ingestion may result in visual disturbances, such as blurred or dimness of Research Gate is an academic social networking site This is an open access article, Research Gate is a European commercial social networking site for scientists and researchers After leaving the HT CO converter, the process gas cools down as it passes through the waste ethanator trim heater in . The temperature f the LT CO converter, normally 205°C, is controlled by the process gas bypass . As for the HT CO converter, the optimum inlet temperature, i.e. the inlet ure at which CO slip is at a minimum, depends on the actual catalyst activity. With a fresh catalyst it is normally best to operate at a temperature somewhat lower than the design temperature. As the catalyst ages, the inlet . The normal 250°C; do not exceed the reactor design temperature of 300°C. The temperature increase should be around 24°C, depending on the conversion in the HT CO converter and on the steam/dry gas ratio. Condensing steam is harmful the inlet temperature should always be at least 15-20°C above the dew point of the gas. There is a risk that condensate will form on th surface of heat exchangers. Residual CO During normal operations, the CO content outlet 11-R-205 should be approximately 0.33 dry mole%. To evaluate the activity of the LT shift catalyst, follow the same procedure as described above. anol Emissions on the Acute exposure of humans to methanol by inhalation or ingestion may result in visual disturbances, such as blurred or dimness of vision, leading to blindness. damage, specifically permanent motor dysfunction, may also result. with methanol can produce mild dermatitis in humans. Tests involving acute exposure of rats, mice, and rabbits have demonstrated methanol to 27th Mar. 2022 Research Gate is an academic social networking site ite for scientists and researchers reactor design temperature of 300°C. The temperature increase should be around 24°C, depending on the conversion in the HT CO converter and on the steam/dry gas ratio. to the catalyst, so the inlet temperature should always be at least 20°C above the dew point of the gas. There is a risk that condensate will form on the cold During normal operations, the CO content outlet 205 should be approximately 0.33 dry mole%. To evaluate the activity of the LT shift catalyst, follow the same procedure as described vision, leading to blindness. Neurological damage, specifically permanent motor nction, may also result. Contact of skin e mild dermatitis in Tests involving acute exposure of rats, mice, and rabbits have demonstrated methanol to
  • 5. www.researchgate.net 27th Mar. 2022 Research Gate is an academic social networking site This is an open access article, Research Gate is a European commercial social networking site for scientists and researchers have low acute toxicity from oral or inhalation exposure, and moderate acute toxicity from dermal exposure. Chronic Effects Chronic inhalation or oral exposure to methanol may result in headache, dizziness, giddiness, insomnia, nausea, gastric disturbances, conjunctivitis, visual disturbances (blurred vision), and blindness in humans. Elevated levels of liver enzymes and decreased brain weight were observed in rats chronically exposed to methanol via gavage (experimentally placing the chemical in the stomach). EPA has not established a Reference Concentration (RFC) for methanol. The Reference Dose (RfD) for methanol is 0.5 milligrams per kilogram body weight per day (mg/kg/d) based on increased liver enzymes (SAP and SGPT) and decreased brain weight in rats. The RFD is an estimate (with uncertainty spanning perhaps an order of magnitude) of a daily oral exposure to the human population (including sensitive subgroups) that is likely to be without appreciable risk of deleterious non cancer effects during a lifetime. It is not a direct estimator of risk but rather a reference point to gauge the potential effects. At exposures increasingly greater than the RfD, the potential for adverse health effects increases. Lifetime exposure above the RfD does not imply that an adverse health effect would necessarily occur. Effect on Ozone Layers Ground-level ozone is formed from nitrous oxides under the influence of the ultraviolet (UV) radiation of the sun. Nitrogen dioxide (NO2), emitted by combustion processes into the at mosphere, is split by UV radiation into nitrogen monoxide (NO) and an oxygen atom. This atomic oxygen combines with an oxygen molecule, forming ozone (O3): Methanol is a widely used solvent and a potential fuel for motor vehicles. Following Methanol product are dangerous for Ozone Layer. Besides environmental aspects, there is also an economic driver to reduce methanol formation by the process, at least to the extent that additional costs are not prohibitive. Methanol formation in the CO shift consumes hydrogen which would otherwise be used to make ammonia. In broad terms, every tone of methanol that is formed (and not recovered to the reformer feed via the process condensate stripper) results in a loss of 1.1 tone of ammonia. This loss in its own right can be a powerful incentive for installing a selective LTS catalyst such as KATALCOJM 83-3X. In addition, methanol is an oxygen containing component which must be removed from the process gas before it is fed to the ammonia synthesis. This removal is normally achieved in the Methanation by reaction with hydrogen. Stripping of process condensate is a very economical way to reduce the methanol content in the process condensate to make it ready for reuse as make-up water to the demineralization unit, thus reducing raw water consumption. Comparison of Operating Costs If the ammonia plant is coupled to an adjacent urea plant, the majority of the methanol containing CO2 stream is used as feed to the urea plant. In such a situation it does not lead to emissions during normal operation of the complex. If the authorities allow emissions for the limited amount of time of the year whilst the urea plant is not in operation, an “end-of-pipe” methanol reduction system as described above might be designed only for the quantity of CO2 vented during normal operation. This allowance can lead to a significant cost advantage when compared to the systems described above which are fully integrated into the ammonia process and which ensure a low methanol concentration for the full amount of CO2. In this case they have to be designed for the full flowrate of process gas, with no reduction in size being possible. The economics of a process which absorbs the methanol from the CO2 stream
  • 6. www.researchgate.net 27th Mar. 2022 Research Gate is an academic social networking site This is an open access article, Research Gate is a European commercial social networking site for scientists and researchers downstream the regenerator in the CO2 removal unit, depends on the following decisions: For a simple system, there is just a bleed stream and a make-up by fresh water. Possibly, the CO2 of stream 8 is cooled below ambient temperature to condense as much liquid as possible. A more complex system would contain an additional absorber installed in stream no. 9 and a desorption for example by sending the water to the already existing condensate stripper. If an “end-of-pipe” system has to be designed for the maximum possible amount of CO2 vented, it will need to operate at 5 to 6% of capacity most of the time (basis: 2,200 MTPD ammonia plant with a 3,500 MTPD urea plant) and will experience 100% load only a few times per year. The favored option might be different for a new project than a retrofit. In the first case, one is free to design the plant right from the beginning for low emission figures. In the latter case, it can be difficult to accommodate changes in process temperatures due to limitations in space for additional equipment or availability of utilities Emission reductions inevitably require additional investment and lead to increased energy consumption. With the exception of the benefits that can be obtained through the use of use of selective LTS catalysts, there is little economic incentive to reduce methanol emissions. None of the removal or abatement systems convert the methanol into a valuable product, but all of them consume energy, as highlighted in Table 1. Sr. No. Parameters Observation &Results 1 Lower temperature at condensate separator (cooling with CW) More condensate to be stripped. More cooling water needed 2 Lower temperature at condensate separator (cooling with chillers) More condensate to be stripped. More cooling water needed Chilling duty is needed (electric power / steam) 3 Catalytic methanol removal at vent Methanol is combusted and CO2 is formed by this process Air blower needed (electric power) Table -1
  • 7. www.researchgate.net This is an open access article, Research Gate is a European commercial social networking s Table –2 How to Control Methanol formation in ammonia plant The Methanol comes in urea plant by CO It is 80% separated by CO2 compressor 1 3rd stage separators.20 % carryover through CO and it goes to waste water section, treated water waste contains about 150-200 ppm methanol. it is very dangerous for cations and anaions resin, it can damage resins. Shift reaction in Line carried out three steps (HT/MT/LT) an line-2 2 Two steps (HT/LT) no MT is line Urea line-2 HT inlet/outlet temperatures are 355/430 degree cent. Iron oxide catalyst is used. In LT Cu based catalyst is used, Inle temp are-195/212 degree cent . Sulpher & Chlorides are poison for catalyst. Chromium based catalyst on top of the first bed, which will act as a chlorine guard catalyst, while the remaining will be made up of alumina based Research Gate is an academic social networking site This is an open access article, Research Gate is a European commercial social networking site for scientists and researchers How to Control Methanol formation in The Methanol comes in urea plant by CO2 rout. compressor 1st ,2nd & stage separators.20 % carryover through CO2 and it goes to waste water section, treated water 200 ppm methanol. it is very dangerous for cations and anaions resin, ins. Shift reaction in Line -1 ed out three steps (HT/MT/LT) and that of 2 2 Two steps (HT/LT) no MT is line-2.In 2 HT inlet/outlet temperatures are 355/430 degree cent. Iron oxide catalyst is used. In LT Cu based catalyst is used, Inlet/outlet 195/212 degree cent . Sulpher & Chlorides are poison for catalyst. Chromium based catalyst on top of the first bed, which will act as a chlorine guard catalyst, while the remaining will be made up of alumina based catalyst. The catalyst consists of oxides of copper, zinc, and chromium or alumina. Reading for methanol in Urea line Fertilizers Ltd. Vijaipur) 1st separator-2122 ppm 2nd separator-860 ppm 3rd separator-255 ppm Waste water treated water 166 ppm. In urea Line-1 Methanol produced very less. Here the three CO shift converter are used. The methanol generally unwanted by LTS CO shift converter. when catalyst activity of LTS goes down it can be formed it can be controlled by LTS catalyst. developed by both the M/S Haldor Topsoe (Catalyst LK-821-2, LK823) is promoted by caesium which efficiently reduced 27th Mar. 2022 Research Gate is an academic social networking site ite for scientists and researchers onsists of oxides of copper, zinc, and chromium or alumina. in Urea line-2 (National Waste water treated water 166 ppm. ol produced very less. Here the three CO shift converter are used. unwanted by product in LTS CO shift converter. when catalyst activity of LTS goes down it can be formed it can be The LTS catalyst developed by both the M/S Haldor Topsoe 2, LK823) is promoted by caesium which efficiently reduced
  • 8. www.researchgate.net This is an open access article, Research Gate is a European commercial social networking s MeOH. The methanol is inversely proportional to temperature. M/S Haldor topsoe and KBR developed advance catalyst if problem then contact to licenser and catalyst may be changed. The MeoH generally formed predominately over the LTS catalyst and part of it end in the process condensate stripper. Following are the method to reduced by methanol 1. Temp of LTS to be minimum 2. Reduced catalyst Volume. 3. Catalyst promoters to be used 4. Avoid Aged catalyst. 5. CO concentration should be lower in LTS feed. Fig- 3 Research Gate is an academic social networking site This is an open access article, Research Gate is a European commercial social networking site for scientists and researchers The methanol is inversely proportional to temperature. M/S Haldor topsoe and KBR developed advance catalyst if problem then may contact to licenser and catalyst may be changed. The MeoH generally formed predominately over the LTS catalyst and part of it end in the process reduced by- product emp of LTS to be minimum. Catalyst promoters to be used. CO concentration should be lower in 6. Lower operation pressure. 7. High Steam/dry gas ratio 8. Higher space velocity the methanol concentration leaving the HTS catalyst is close to equilibrium and therefore independent of catalyst type, methanol formation in LTS catalysts is kinetically limited and does not usually reach equilibrium. As the methanol forming reaction is exothermic, and HTS catalysts operate at higher temperature and at high temperature methanol formation is less shape of the equilibrium curve dictates that methanol formation across HTS catalysts is substantially less than that across traditional, nonselective LTS catalysts (Figure 3). 27th Mar. 2022 Research Gate is an academic social networking site ite for scientists and researchers Lower operation pressure. High Steam/dry gas ratio. methanol concentration leaving the HTS catalyst is close to equilibrium and therefore independent of catalyst type, methanol formation in LTS catalysts is kinetically limited and does not usually reach equilibrium. As the methanol forming hermic, and HTS catalysts operate at higher temperature and at high temperature methanol formation is less the shape of the equilibrium curve dictates that methanol formation across HTS catalysts is substantially less than that across traditional, catalysts (Figure 3).
  • 9. www.researchgate.net This is an open access article, Research Gate is a European commercial social networking s LTS catalyst is slightly unusual in that selectivity increases, and by-product formation decreases, as the catalyst ages (Figure 4). This behavior is because the activity with regard to methanol synthesis declines as the active sites Fig-4 Process Condensate Treatment The gas leaving the LTS is cooled and condensate is removed via the process condensate separator. The split of methanol is determined by vapor-liquid equilibrium, hence the lower the temperature, the greater the proportion of methanol that is removed via t process condensate, as illustrated in Figure 5. Modern plants, and older plants retrofitted with condensate strippers in the last couple of decades, use a medium pressure stripper to treat the condensate. A well designed stripper meets Research Gate is an academic social networking site This is an open access article, Research Gate is a European commercial social networking site for scientists and researchers LTS catalyst is slightly unusual in that product formation Figure 4). This is because the activity with regard to methanol synthesis declines as the active sites for methanol synthesis decrease. There is no corresponding impact on the activity with regard to the shift reaction, which, in a well catalyst, remains high enough to maintain an equilibrium CO slip. The gas leaving the LTS is cooled and condensate is removed via the process condensate separator. The split of methanol is liquid equilibrium, hence the lower the temperature, the greater the proportion of methanol that is removed via the in Figure 5. Modern plants, and older plants retrofitted with condensate strippers in the last couple of decades, use a medium pressure stripper to treat the condensate. A well designed stripper meets most environmental standards for waste water and will recycle methanol to the reformer feed. Plants with older designs of stripper can use LP stripping to remove methanol and ammonia from the condensate. Sometimes they are vented to atmosphere along with the stripping ste more commonly the vent stream is condensed and sent, for example, to a feed coil saturator (although sometimes a small, methanol containing stream is “purged” to atmosphere). 27th Mar. 2022 Research Gate is an academic social networking site ite for scientists and researchers for methanol synthesis decrease. There is no corresponding impact on the activity with regard to the shift reaction, which, in a well-structured enough to maintain an al standards for waste water and will recycle methanol to the reformer feed. Plants with older designs of stripper can use LP stripping to remove methanol and ammonia from the condensate. Sometimes they are vented to atmosphere along with the stripping steam, but more commonly the vent stream is condensed and sent, for example, to a feed coil saturator (although sometimes a small, methanol containing stream is “purged” to atmosphere).
  • 10. www.researchgate.net This is an open access article, Research Gate is a European commercial social networking s Fig-5 Methanol Emission Reduction Overview several options exist for reducing methanol emissions including the following: 1. Reducing the amount that is formed. 2. Removal or decomposition of the methanol within the process. 3. Removal or decomposition at the point of emission. 4. Combination of the above schemes. Reduction of Methanol Formation The amount of by-product methanol produced in the LTS converter is influenced by a variety of factors, which are summarized in Table Sr. No. Increase in Effect on methanol make 1 Steam / H2 ratio Decrease 2 Inlet temperature ↑(if not at equilibrium) ↓(if at equilibrium) Research Gate is an academic social networking site This is an open access article, Research Gate is a European commercial social networking site for scientists and researchers options exist for reducing methanol emissions including the following: ing the amount that is formed. Removal or decomposition of the methanol tion at the point of the above schemes. Reduction of Methanol Formation product methanol produced in the LTS converter is influenced by a variety of in Table 1. In most plants, there is only limited flexibility to change operating conditions with the result that LTS catalyst selection is the only real alternative for reducing methanol by-product formation. Selective low methanol LTS catalysts such as KATALCOJM 83-3X, reduce methanol formation by about 90% compared to conventional non-selective LTS catalysts. As the relative contribution to methanol formation from the LTS falls, that from the HTS increases, and methanol emissions can be grossly underestimated if formation across a selective LTS is considered in isolation Effect on methanol Decrease ↑(if not at equilibrium) ↓(if at equilibrium) 3 Pressure ↑Increase 4 Space velocity ↓Decrease 5 Catalyst age ↓Decrease 6 Catalyst selectivity ↓Decrease 27th Mar. 2022 Research Gate is an academic social networking site ite for scientists and researchers most plants, there is only limited flexibility to conditions with the result that LTS catalyst selection is the only real alternative product formation. Selective low methanol LTS catalysts such as 3X, reduce methanol formation by about 90% compared to selective LTS catalysts. As the relative contribution to methanol formation from the LTS falls, that from the HTS increases, and methanol emissions can be grossly underestimated if formation across a selective LTS is considered in isolation (Figure 6). ↑Increase ↓Decrease ↓Decrease ↓Decrease
  • 11. www.researchgate.net This is an open access article, Research Gate is a European commercial social networking s Table-3(Effect of various operating parameters Fig-6 Separated methanol from CO2 separators used as a bacteria Feed in waste water anaerobic Treatment In CO2 compressor separators about 80% methanol can be used in waste water treatment Research Gate is an academic social networking site This is an open access article, Research Gate is a European commercial social networking site for scientists and researchers (Effect of various operating parameters on methanol production) compressor used as a bacteria Feed in waste compressor separators about 80% methanol can be used in waste water treatment as a Bactria feed as shown in the figure 1st separator contain maximum methanol. 27th Mar. 2022 Research Gate is an academic social networking site ite for scientists and researchers as a Bactria feed as shown in the figure- 7.The separator contain maximum methanol.
  • 12. www.researchgate.net This is an open access article, Research Gate is a European commercial social networking s Fig-7 Conclusion In Urea Plant 1st separator, if pressure and tempearure maintain according methanol separation then you can remove 80 methanol from separators. As with oth organic compounds emissions, methanol emissions from ammonia plants are considered to contribute to ground-level Consequently, in many places of the world, targets and regulations exist to reduce Volatile organic compound emissions. Regu starting to pay more attention to Volatile organic compound emissions on ammonia plants and this trend is likely to increase. Several technical options exist to reduce these emissions, including the following: 1. Reducing methanol by formation in the LTS catalyst. 2. Modifying the CO2 removal process. 3. End-of-pipe solution. Lowest Volatile organic compound can be achieved only by catalytic conversion at the point of emission. However, by Research Gate is an academic social networking site This is an open access article, Research Gate is a European commercial social networking site for scientists and researchers if pressure and tempearure maintain according methanol separation then you can remove 80-85% As with other Volatile emissions, methanol sions from ammonia plants are considered level ozone. s of the world, t to reduce Volatile emissions. Regulators are ing to pay more attention to Volatile organic emissions on ammonia plants and o increase. Several technical options exist to reduce these emissions, Reducing methanol by-product formation in the LTS catalyst. Modifying the CO2 removal process. Lowest Volatile organic compound emissions can be achieved only by catalytic conversion at the point of emission. However, by combining it with the other options, the amount of methanol to be converted in the emission stre reduced. Since the Volatile organic compound emissions are influenced by sev parameters and catalyst properties, one should not prematurely decide on one tech solution. It is recommended to look at the process in close co-operation with the catalyst vendor, CO2 removal licensor, and overall process licensor and contractor, in order to obtain the best overall solution References 1. “Development of a Predictive Kinetic Model for Methanol Formation over Low Temperature Shift Catalysts”, P V Broadhurst, C Park and I Johnston, Proceedings of Nitrogen 2006, Vienna, 12-15 March 2006. 2. United States Environmental Protection Agency, New Source Review (NSR) Improvements: Supplemental Analysis of the Environmental Impact of the 2002 Final NSR Improvement Rules, November 2002 [6] Clean Air Act, Section 112. 27th Mar. 2022 Research Gate is an academic social networking site ite for scientists and researchers tions, the amount of methanol to be converted in the emission stream can be reduced. Since the Volatile organic compound luenced by several process parameters and catalyst properties, one should prematurely decide on one technical solution. It is recommended to look at the operation with the catalyst removal licensor, and overall icensor and contractor, in order to obtain the best overall solution. “Development of a Predictive Kinetic Model for Methanol Formation over Low Temperature Shift Catalysts”, P V Broadhurst, C Park and I ceedings of Nitrogen 2006, United States Environmental Protection Agency, New Source Review (NSR) Improvements: Supplemental Analysis of the Environmental Impact of the 2002 Final NSR Improvement Rules, November 2002 [6] Clean Air Act, View publication stats View publication stats